Photodegradation of typical pharmaceuticals changes toxicity to algae in estuarine water: A metabolomic insight

The ubiquitous existence of various pharmaceuticals in the marine environment has received global attention for their risk assessment. However, rather little is known thus far regarding the natural attenuation (e.g., photolysis)-induced product/mixture toxicity of these pharmaceuticals on marine organisms. In this study, the photodegradation behavior, product formation, and risks of two representative pharmaceuticals (i.e., ciprofloxacin, CIP; diclofenac, DCF) were explored in the simulated estuary water. It was noted that both pharmaceuticals can be completely photolyzed within 1 h, and five products of CIP and three products of DCF were identified by a high-resolution liquid chromatography-mass spectrometer. Accordingly, their photodecomposition pathways were tentatively proposed. The in silico prediction suggested that the formed transformation products maintained the persistence, bioaccumulation potential, and multi-endpoint toxic effects such as genotoxicity, developmental toxicity, and acute/chronic toxicity on different aquatic species. Particularly, the non-targeted metabolomics first elucidated that DCF and its photolytic mixtures can significantly affect the antioxidant status of marine algae (Heterosigma akashiwo), triggering oxidative stress and damage to cellular components. It is very alarming that the complete photolyzed DCF sample induced more serious oxidative stress than DCF itself, which called for more concern about the photolysis-driven ecological risks. Overall, this investigation first uncovered the overlooked but serious toxicity of the transformation products of prevalent pharmaceuticals during natural attenuation on marine species.